Complex salts containing lead phthalate and lead salts of aliphatic acids



Patented Feb. 18, 1947 'COMPLEX SALTS CONTAINING. LEAD -PHIHALATE. ANDLEAD SALTS -OF ALIPHATIC ACIDS hie anaer stewart, jMount'ain Lakes, NJ'., and Adrian E; Eliot; Hemps'tead, and Leonard M. Kebrich, Brooklyn,N. Yr, as'sighor's to National Lead Company, New York, N. Y., acorporation of NewJer'Sey No Drawing. Application Siiteinb'r-il, 1945,

Serial No. 502,067

v:11 Claims.

The present iiive tiea relates it new and usetui cbmplei: saltscontaining lead phthalate "and a'lead "salt bf a nibhbb'as'ic saturatedaliphatic an dbject at the present mvefitien to pr6- 'dnce fio'v'e'ldouble salts hating pigmentary value. such double salts may be employedeither alone or incoinbinatidn with other pigments in formu 'la'tingimproved paint compositions. Other objects will bcoiiie apparent fromthis description -of the invention,

In our co-pending application, Serial *No. 502,- 066, filed September11, 1943, we have described a process for making lead salts of phthalicacid. The present-'ifiveritionis based upon the discovery that'if=stbichi6met'ric quantities of a monobasic saturated aliphatic acidcorresponding to the general formula CfiHiHiCOOfiin which n representsthe number 'of carbon atoms be introduced in the general nithod orpreparing lead phth'alate's disclosed in the said copending application,eomplei': salts will be formed, correspondmg a; til follhwing g neralempirical formulae; which n represents theinumbei er carbon atoms as iiithe eneral formula abovi 4lbCsfi4(CbQ) afib Cni-IghaCOO) a (Type A) PbO2PbCeH4 (CO6) 2Pb'(CiH2'hl-1'GOO)"2 (Type .3)

According to the present invention compounds classifiable under Type Ahave been prepared as follows:

(1-) Tetra-lead phthalate-lead acetate,

as well as compounds classifiable under Type B, as follows:

(5) Basic lead phthalate-le'ad acetate,

PbO -2PbCsH4(COO) a'Pb (Cal-I302) 2 (6) Basic lead phthalate-leadpropionate,

PbO '2PbC6H1(COO) EPb (CsHsOz) 2 (7) Basic lead phthalat e-leadbutyrate,

PbO2PbC6H4(COO) '2'Pb'(C4H1O2) 2 (a) Basic ieea sewa e-lead isebuwrate,'PbO-2l bCsli-;(COO)2-Pb(C4H1O2)2 (9) Basics-lead phthalate-leadcaproate, PbbP'iiGeHilCOOwPbwei Inom "(10) Basie lead phthalate-leadcaprylate,

-PbO-2PbCI-I4(COO)2-Pb(CioH19Oz)2 cursas'ie ieaa emanate-ma ae'aat.statement-camera(cameos:

- 112) Basic lead phthalate-lead a ethylbutyrate,

fitdfibintcbiiii-fifir(att nuation; eel-ri ening; aha-then method'soimanureeture, own above classified as Type B are more particularlydescribed and elaimed in our divisional co-pending application,SerialNQIGSQ- 802,'fi1ed March 15, 194 6.

It will be noted from the above enumerated compounds that "tl'rpresehtinvention is applicable for the preparation of complex lead salts*of phthalic S ill and normal, isomeric and substituted monobasicsaturated aliphatic acids. a V

The method of the presentinvention comprises bringing togethe r -i naqueous media the primary reactants: lead monoxide, phthalic ;acid, oranhydride, and the monobasic acid, whereby a reaction oecurs withsubstantially complete recovery ofjhe complex lead compound in theiormof a white precipitate which is sparingly soluble w r-n The manner ofbringing the primary reactants together inthe aquepus media is notcritical. For

instance, the pnthalic acid (which expression is meant toincludephthalicanhydride) may be dis solved in hot waterand the hotsolution added gradually, preferably with stirring, to an aqueoussuspension of lead monoxide and saturated aliphatic acid, or thereactants may simply be mixed with water. Qccaslonally it may be founddesirable to charge the reactants, mixed with water, into a ball, erpebble, mill or similar apparatus in which the reaction isauowea to takepiece;

The reaction may be carried out at any convenient temperature betweenabout 15 'C. and C.- In selecting the ma ner 6f mixing the reactantstogether and the temperature at which the reaction is to" be carried outthe character of the monoba s i'c saturated aliphatic acid should beconsidered. Where, as is the case in compdunds 1-8, inclusive, listedabove, the saturated aliphatic acid is water soluble, a ball mill needwith water in any suitable vessel. In such case the employment ofanelevated temperature, say

between about 75 Cmand about 95 C., hastens completion of the reaction.However, where the saturated aliphatic acid is not soluble in water butremains solid or gummy, as is the case with compounds 9-12, inclusive,listed above, it is preferable to charge the reactants mixed with waterinto a ball or pebble mill and conduct the reaction at room temperature,say between about .C and C. When an elevated temperature is emnot beemployed, b'ut the reactants maybe mixed ployed the reactants are .keptin contact with each other in the aqueous media,-preferably underagitation, until the reaction is completed which usually requiresbetween about 3 hours and about 8 hours. When the reaction is carriedout at room temperature, a longer period of time is generally required,sometimes as much as 18 or 20 hours.

The following examples are given to illustrate, but not to limit thepresent invention.

7 HEXMLEI Lead phthalate-Zead acetate, 4PbCaH4(QQz-) z'Pb (CzHaOz) 289.3 grams (.4 mol) of finely powdered lead monoxide, PbO, weresuspended in 1200 cc. of water, containing 12 grams of 80% acetic acid,(equivalent to .08 mol of acetic anhydride) The suspension was agitatedand heated to 70'80 C. A solution of'phthalic, acid prepared bydissolvin 47.4 g'rams(.32 mol) in"'500 'cc." of boiling water wasgradually added tothe suspension over a five hour period. The resultantwhite product was filtered, washed with-2'liters of hot water, and

dried at 85 C. The yield was substantially complete; theproductcontained 82%1ead phthalate ,andl8l% 'lead acetate. Its specific gravitywas 350111191 fiQ' 3 4.5-

EXAMPLE -2 Basic lead ph'thaZate-Zead acetate- PbO ZPbCGH ((COz) 2P6(CzH 302) 2 89.3 grams -(.4mol) of finely powdered lead monoxide, PbO,were suspended in 1200 cc.of water containing 15-grams of 80% aceticacid "(equivalent to .-1-mol of acetic anhydride). The "suspension wasagitated and heatedto IO-80 C. A solution of phthalic acid made bydissolving 29.6 grams (.2 mol)' of phthalic anhydride in 300 'cc. ofboiling water was gradually added'to the suspension over a five hourperiod. 4 The resultant white product was filtered, washed with 2 litersof hot water, and dried at 85 C. The yield was substantiallycompleterand the product contained 57.5% lead phthalate,'-25.2% leadacetate and 17.3% of combined basic lead oxide. Its specific gravity wasfound to be 3.73.

EXAMPLE 3 Lead phthaZate-lead prorn'onate- 4PbCaH4 (COzMPb (CaHsOz) z ,Asuspension containing 89.3 grams of finely powdered lead monoxide, PbO,in 1200 cc. of .water containing 12.15 grams of 97.56% propionic acidwas agitated at 70-75 C. and treated over a five hour period with asolution of phthalic acid prepared by dissolving 47.37 grams of phthalicanhydride in 500 cc. of boiling water. ,The white product, afterfiltration, washing and drying at 85?; C.- contained 80.8% leadphthalate and 19.2% lead propionate. It was electrostatic, and itsspecific gravity was found to be 3.235.

EXAMPLE 4 Basic lead phthalate-lead propionaiw PbO 2PbCsH4(CO2) zPb(CsHsOz) 2 A suspension containing 89.3 grams of finely powdered leadmonoxide, PbO, in 1200 cc. of water containing 15.60 grams of propionicacid. was agitated at 70-75 C. and treated over a five hour period witha solution of phthalic acid prepared by dissolving 29.6 grams ofphthalic anhydride in about 300 cc. of boiling water. The white product,on filtration, washing and drying at 85 C. contained 56.3% leadphthalate, 26.8% lead propionate and 16.9% of combined basic lead oxide.Its specific gravity was found to be 3.32.

EXAMPLE 5 Basic lead phthaZate-lead butyrate- PbO' ZPDCsHAC'Oz) zPb(C4H702) 2 89.3 grams of finely powdered lead monoxide was added to 1200cc. of water containing 17.6 grams of normal butyric acid. The mixturewas agitated and heated to 70-75" C. A solution of phthalic acidprepared by dissolving 29.6 grams of phthalic anhydride in 600 cc. ofboiling water was added to the hot suspension of lead oxide over a fivehour period. The white product on filtration, washing and drying at 85C. contained 55.1% lead phthalate, 31.2% lead butyrate and 13.7% ofcombined basic lead oxide. Its specific gravity was found to be 3.15.

EXAMPLE 6 I Basic lead phthalate-Zead isobutgjrate- 7 P 2PbCsH4 (CO2)zPb (C4H7O2) 2 EXAMPLE 7 Lead Phthalate-lead butyrate- 4PbC'sH4 (CO2)2Pb(C'4H702) 2 89.3 grams of finely powdered lead monoxide was addedto1200 cc. of water containing 14.2

grams of 99.5%normal butyric acid. The mixture was agitated and heatedat 70-75 C. A solution of phthalic acid prepared by dissolving 47.4grams of. phthalic anhydride in 500 cc. of hot water was added to thehot suspension over a five hour period. The white product, on filtrationand drying at 85 C. contained 79.6% lead phthalate and 20.4% leadbutyrate. Its specific gravity was found to be 3.01.

EXAMPLE 8 Lead phthalate-lead isobutyrate- 4PbCcH4(C'O2) 2'Pb(C4H7Oz) 289.3 grams of finely powdered lead monoxide was added to 1200 cc. ofwater containing 14.4 grams of 98% isobutyric acid. The mixture wasagitated and heated to IO-75 C. A solution of phthalic acid made bydissolving 29.6 grams of phthalic anhydride in 600 cc. ofboiling waterwas .lead"phthciate ladicoprod hours at room temperature (15-20=C.)

gravity was found to be 2.61.

added to themot-suspension.of. ,leadoxide over a period of fivehc rs;Thewhite product, on fil- 13.7 ofqdqmbined basic. lead exideravitywasfoundtdbeBIITL f a w n amaaa ratggfiigam owdereaaead phthalicanhydride, 17.4

monoxide, 22.2-gram I grams of caproic acid ahdBOO cc. of water was-'-"F laceii 'in a pbble m'ill and groiiird mor't l firiihours at roomtemperature (15 203 product which was obtained in C. p k a completeyield contained no uncombined lead phthalate and did not soften or meltwhen dried at 90 C. Its spef cific gravity was found to be 2.86. a

I EXAMPLE" A 'Basic lead phthclate-lead calm/late?- PbO 2Pb C6H4(CO2')zPb(C1aH19O2) z A charge comprising 67 grams of powdered lead monoxide,22.2 grams of phthalic anhydride,

: tnati'on, 'rwashmgsand' dnymgiifat i85 v.cC."loontaine'd 55.1% leadphthalate, 31.2% 'leaehisobiityrate and lts specific foregoing "aresiipstan tially in'scl f 7 M y, 7 pie, mixtures containing monobasiciead phthale o 1am? in ey be p pa byusing lead monoxide, phthalicanhydride,:and c acifdin th'erespective molar 2. Mixtures of compounds'oFTypeAwith normal leadgiphthalateflmayiibciplicnared by using -leadmon ide, .phthali a hyd e a da h acid "in fine ,;respectiremolar ropor ti ons' of f'nzn lz2wherefnis 5 or "greaterthan ,5. ithas been found thatcompoundsofTypeEBcohtain the least aniounts of leadmionoxidezandphthalic acid required to produce insolublecomplex lead I compounds=contai-ning substantially all the aliphatic'acidpos sible 'e system.

tully describes and illustrates the present invention, it will beappreciated by those skilled in the artthat various modifications may bemade within the scope of; the appended claims.

We claim:

1. Azprocess for preparing complex lead salts which comprises mixingtogether in aqueous me- 21.6 grams of caprylic acid and 300 cc. of waterEXAMPLE Basic lead ph'thoZate-Zedd' stearote PbO 2PbCsH4 (CO2)(CHI-13502) 2 monoxide, 22.2 grams'of phthalic anhydride, 42.6

grams ofstearic acid and 300 cc. of water was placed in a pebble milland groundfor'40 hours at room temperature (15-20? C.).' The whiteproduct, obtained incomplete yield, contained no uncombinedstearic acidor leadphthalate, and

did not soften or melt when dried at "90C- Its. specific gravity wasfound to be 2.03.

ExAiv PLa- 12 17.4grams of 2 ethylbutyric acid and 300 cc. of

tion is substantially; complete. I a

, 3.1A process according to claim Iwherein the molar ratio of leadmonoxide to phthalic acid dia lead monoxide, phthalic acid and amonobasic aliphatic acid corresponding to the general formula CnHn+1COOH in which n represents the 'nurnber'of carbon atoms, in amountssuch that forrevery 2 molarparts of aliphaticacid, there are presentbetween 2 and 4 molar parts of phthalic acid and between land 5 molarparts of lead monoxide, and while agitating the mix-" I ture maintainingthe temperature thereof b'e-. tweenabout' 15 C. and 100 C.

until thereaction is substantially complete.

, g 2. A process'for preparing complex lead salts which comprisesmixing. together in aqueous a media lead monoxide,phthalic acid andamonoa I v r basic aliphatic acid selectedfrom the groupcon A chargecomprising 67 grams of powdered lead 1 sisting of acetic, propionic,butyric, isobutyric,

caproic, caprylic,'and stearic acids in amounts I such that for'every 2molar parts of, aliphatic acid there are present between 2 and 4 molarparts of phthalic acid and between 4 and 5 molar parts of leadmonoxide,and while agitating the mixture maintainin'g the temperature thereof"between about 15 C. and 100. C. until the reac!- to aliphatic acid issubstantially'5 :'4:2.-

I monoxide water was placed in a pebble mill and ground for 16 hours atroom temperature. The resultant white product obtained in completeyield, contained no uncombinedflead phthalate and did not soften or meltwhendried at 90 C. Its specific gravity was found to be 3.02. i

In preparing the complexileadcompounds of the present invention, thereactants are used'in the stoichiometric proportionsindicatedby theformulae for TypeA and TypeB compounds. The use of proportions otherthan' these may result inproducts representing incomplete recovery ofthe monobasic acid, or the lead phthal ate, or both.

The invention contemplates thepreparation of products which are mixturesof ype Acornpounds with Type B compounds aswell as mix- I I turescontaining leadphthalates, all of which 4. A process according to claim1 wherein the aliphatic acid is acetic acid and the ratio of lead 5. Aprocess according to claim 1 wherein the aliphatic acid is 'propionicacidand the ratioof lead monoxide to phthalic acid to aliphatic acidaliphatic acidis isobutyric acid and theratio of I lead monoxide'tophthalic acid to aliphatic acid I .7. Asa new product acomplexleadsaltcom-' prising lead phthalate and the lead salt of a.

monobasic saturated aliphatic acid correspond ing to the general formulaCnH2h+1CoOH in which n represents thenumber of carbon atoms. 8. Acomplex lead salt corresponding to the empirical formula giPbR-PbXz',where R is the w phthalic'acidradical'and X is thehradical of a1]monobasic saturated aliphatic acid corresponding to the general formulaCnH2n+lCQOH, in i which n represents the number of carbon atoms. I

v9. As a new. product the complex'lead phthalw ser. i

to'phthalic acid to aliphatic acid is v empiricaliormulaz Y 2 ate-leadacetate salt corresponding; ;tp tpg empirical formula z. r 2 V.ate-le'ad ispbutyrate salt corrgspongimg to; the

emp al m i, 4PbCeH4(COO) z-PMCaI-IqCOO):

Y -E 9 SQ IE J V L The following references: are 0f. record in the fl1eof;th is patent: 1

Numb r" Date ER- REFERENCES ADRIAN R. ,P11'Ro'r. 1 LEONARD M; KEBRICH. r

vol. 148, pp. 66 and 617.

